Semiconductor device with silicon dioxide layers formed using atomic layer deposition

ABSTRACT

Improved methods are disclosed for catalyst-assisted atomic layer deposition (ALD) to form a silicon dioxide layer having superior properties on a semiconductor substrate by using a first reactant component consisting of a silicon compound having at least two silicon atoms, or using a tertiary aliphatic amine as the catalyst component, or both in combination, together with related purging methods and sequencing.

RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.10/459,943, filed on Jun. 12, 2003, which relies for priority uponKorean Patent Application No. 02-39428, filed on Jul. 8, 2002 and KoreanPatent Application No. 03-6370, filed Jan. 30, 2003, the contents ofwhich are herein incorporated by reference in their entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to improved methods for growingsilicon dioxide layers on substrates, such as in semiconductormanufacture, using atomic layer deposition processes. The methods ofthis invention facilitate exercising extremely precise control over theproperties of a silicon dioxide layer applied, for example, to a gateoxide or a dielectric layer. The methods of this invention haveparticular utility in fabricating gate spacers, gate oxides, silicideblocking layers, bit line spacers, inter-level dielectric layers, etchstoppers, and related final or intermediate products in semiconductorfabrication.

2. Description of the Related Art

In manufacturing a semiconductor device, a silicon dioxide layer istypically formed on a substrate surface by such conventional techniquesas chemical vapor deposition (CVD), low-pressure CVD (LPCVD), orplasma-enhanced CVD (PECVD). These techniques are recognized asproviding a good step coverage at a comparatively low temperature. Asthe density of a semiconductor device increases, however, so too do theheights of the respective elements which comprise the device. As aresult, a problem arises due to increased pattern density variation anda corresponding decrease in uniformity.

As taught in U.S. Pat. No. 6,090,442 (Klaus '442), which patent isincorporated herein by reference, one approach to these recognizedproblems was to use an atomic layer deposition (ALD) technique. Klaus'442 teaches, however, that the big drawback to ALD techniques was thatthey typically required temperatures greater than 600° K. and reactantexposures of greater than 10⁹ L (where 1 L=10⁻⁶ Torr sec) for thesurface reactions to reach completion. Such high temperature and highexposure procedures are not desirable for ultra-thin film depositionapplications for various reasons including the difficulty of carryingout such procedures.

An improved approach to such problems was taught by the Klaus '442patent. Klaus '442 provides a method for growing atomic layer thin filmson functionalized substrates at room temperatures utilizing catalyzedbinary reaction sequence chemistry. More particularly, according to theKlaus '442 patent, a two-step atomic layer deposition (ALD) process,using two catalyst-assisted “half-reactions” carried out at roomtemperature, can be used to grow a silicon dioxide film on an OHterminated substrate.

In a specific embodiment, Klaus '442 utilizes SiCl₄ as a “firstmolecular precursor” and pyridine as a catalyst. First, the substrate isfunctionalized with OH⁻ as a “first functional group,” for example usingH₂O. Next, the functionalized substrate is exposed to a catalyst that isa Lewis base or Lewis acid (e.g., pyridine) and a first molecularprecursor which includes the primary element of the film to be grown aswell as a second functional group (e.g., SiCl₄). As described by Klaus'442, in the first “half-reaction,” the catalyst interacts with thefirst functional group of the functionalized substrate; then, the firstmolecular precursor reacts with the first functional group (which hasbeen activated by the catalyst) resulting in a displacement of thecatalyst and a bond between the first functional group of the substrateand the primary element of the first molecular precursor. Takentogether, these two reactions comprise the first “half-reaction” andrepresent the beginning of film formation with the second functionalgroup now located across the surface of the film.

At this point in the Klaus '442 process, excess first molecularprecursor and any byproducts are purged from the reaction chamber, andthe partially-reacted substrate is exposed to additional catalyst and asecond molecular precursor. The catalyst activates the exposed secondfunctional group along the surface of the film by reacting with it andwith a second molecular precursor, resulting in a displacement of thesecond functional group and also resulting in a bond to the primaryelement of the first molecular precursor. Now, the second molecularprecursor reacts with the bond between the primary element of the firstmolecular precursor and the catalyst resulting in a displacement of thecatalyst and the deposition of the first functional group on thenewly-grown surface layer, thereby completing a full growth/depositioncycle and restoring the substrate surface to a functionalized state inpreparation for the next cycle.

Although the catalyst-assisted deposition processes of the Klaus '442patent represent substantial advances in ALD technology, and do makepossible room-temperature ALD, it has been found that the surfacedensity, uniformity and quality of thin films grown using the Klaus '442technique will not meet increasingly demanding standards in thesemiconductor industry. With the seemingly never-ending evolution towardever-smaller microelectronic components, ever-more precise control isrequired over the properties of semiconductor devices. Such precisioncontrol requires increasingly highly uniform surface properties andpattern density. It has now been found that novel improvements in ALDtechniques in accordance with this invention produce thin films forsemiconductor devices having superior surface density and significantlymore uniform surface properties than could be achieved with prior artmethods resulting in surprisingly more precise control over theproperties of a thin film layer and in higher quality semiconductordevices suitable for modern miniaturization applications.

The Klaus '442 patent represents that: “Strong amine bases liketriethylamine ((C₂H₅)₃N) have been shown to form salt compounds liketriethylammonium chloride (NH+(C₂H₅)3Cl—) in the presence ofchlorosilanes. These salts could poison the surface and degrade thereaction efficiency as they build up.” (column 9, line 24˜28). Thus,Klaus '442 appears to teach away from the presence of triethylamine,i.e. tertiary aliphatic amine, in ALD applications. But, in thisinvention, control of process conditions coupled with a variety of purgemethods have been found to solve the above problems.

OBJECTS OF THE INVENTION

Accordingly, a general object of this invention is to provide improvedmethods for using atomic layer deposition (ALD) to grow highly uniformthin films having superior surface density, extremely high purity, andwith highly precise control of surface properties.

A further object of this invention is to provide ALD methods for formingsilicon dioxide layers on a semiconductor substrate using siliconcompounds having at least two silicon atoms as one of the reactantmaterials.

Still another object of this invention is to provide ALD methods forforming silicon dioxide layers on a semiconductor substrate usingtertiary aliphatic amine compounds as a catalyst material.

Yet another object of this invention is to provide optimum temperatureand pressure ranges for carrying out the methods of this invention.

Another object of this invention is to provide reaction/purging processsequences, and timing and techniques for carrying out such depositioncycles, to enhance the benefits of the methods of this invention.

Still another object of this invention is to provide methods forhardening a silicon dioxide thin film formed on a substrate by themethods of this invention.

Yet another object of this invention is to provide improvedsemiconductor devices having a substrate with a silicon dioxide layerwhich has superior surface density and is of extremely high purity anduniformity deposited along a surface of the substrate for use in suchapplications as gate spacers, gate oxides, silicide blocking layers, bitline spacers, interlevel dielectric layers, etch stoppers, and the like.

A specific object of this invention is to provide catalyst-assisted ALDmethods for forming silicon dioxide layers on a semiconductor substrateusing Si₂Cl₆ as the first reactant, or using a tertiary aliphatic amineas the catalyst, or both.

These and other objects, advantages and improvements of the presentinvention will be better understood by the following description whichis to be read in conjunction with the several Figures and Drawings asdiscussed hereinafter.

SUMMARY OF THE INVENTION

The invention consists of improved methods for using catalyst-assistedatomic layer deposition (ALD) to form silicon dioxide thin films havingenhanced properties and purity on semiconductor substrates. In oneinvention embodiment, a silicon compound having at least two siliconatoms, e.g., Si₂Cl₆, is used as the first reactant in an ALD process. Ina second invention embodiment, a tertiary aliphatic amine compound,e.g., trimethyl amine, is used as the catalyst in an ALD process. In athird invention embodiment, a silicon compound having at least twosilicon atoms is used as the first reactant and a tertiary aliphaticamine is used as the catalyst in an ALD process. In other inventionembodiments, methods for hardening the deposited silicon dioxide thinfilms are provided, optimum temperature and pressure conditions forcarrying out the methods of this invention are established, andalternative reaction/purging process sequences for the methods of thisinvention are described.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow chart that schematically illustrates the steps of theALD methods of this invention for forming a silicon dioxide thin film ona substrate.

FIG. 2 is a schematic illustration of the several chemical reactionsteps, showing what is theorized to be the underlying chemistry, onwhich the improved ALD methods of this invention are based.

FIG. 3 compares the silicon dioxide deposition rate on a substrate foran ALD method according to this invention with that for a prior art ALDprocess.

FIG. 4 compares the silicon “richness” of a thin film SiO₂ layer formedon a substrate using an ALD method according to this invention with thatfor a prior art ALD process.

FIG. 5A compares the silicon bonding status of silicon in a SiO₂monolayer formed using an ALD method according to this invention withthat for a prior art ALD process. FIG. 5B schematically illustrates whatis theorized to be the different silicon chemical bonding arrangementswhich account for the differences in bonding status established by FIG.5A.

FIG. 6 compares the wet etch rate of a SiO₂ thin film formed using anALD method according to this invention with that for a prior art ALDprocess.

FIG. 7 is a chromatograph confirming the formation of unwantedparticulate byproducts having Si—N bonds when an ALD process is carriedout according to prior art teachings using a catalyst containing one ormore N—H bonds.

FIG. 8 illustrates a gas pulsing method of supplying reactant andcatalyst feeds to the reactant chamber in accordance with one embodimentof this invention.

FIG. 9-12 illustrate alternative possible representative “recipes” orsequencing cycles for gas pulsing/pumping and/or purging to be used incarrying out ALD methods in accordance with this invention.

FIG. 13 illustrates how the SiO₂ deposition rate on a substrate using anALD method in accordance with this invention varies in relation toprocess temperature.

FIG. 14 illustrates how the impurity content (as measured by carbonpresent) of a SiO₂ thin film formed using an ALD method in accordancewith this invention varies in relation to process temperature.

FIG. 15 illustrates how the SiO₂ deposition rate on a substrate using anALD method in accordance with this invention varies in relation toprocess pressure.

FIG. 16 illustrates how the non-uniformity of a SiO₂ thin film formedusing an ALD method in accordance with this invention varies in relationto process pressure.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Table 1 below is a summary comparing the theoretical chemical reactionsunderlying the prior art high-temperature ALD technique and thecatalyst-assisted ALD technique of the Klaus '442 patent with threeillustrative embodiments of the present invention, as describedhereinafter. TABLE 1 High-Temperature ALD Si—OH* + SiCl₄ →Si—O—Si—Cl₃* + HCl Si—Cl* + H₂O→ Si—OH* + HCl Klaus ′442 patent Si—OH* +C₅H₅N + SiCl₄ → Si—O—Si—Cl₃* + HCL + C₅H₅N Si—O—Si—Cl₃* + C₅H₅N + H₂O →Si—O—OH* + HCl + C₅H₅N Present Invention: Si—OH* + Si₂Cl₆ + C₅H₅N 1stex. embodiment → Si—O—Si(Cl₂)—Si—Cl₃* + HCl + C₅H₅NSi—O—Si(Cl₂)—Si—Cl₃* + C₅H₅N + H₂O → Si—O—Si—O—Si—OH* + HCl + C₅H₅NPresent Invention: Si—OH* + SiCl₄ + R₃N 2nd ex. embodiment →Si—O—Si—Cl₃* + HCl + C₅H₅N Si—O—Si—Cl₃* + R₃N + H₂O → Si—O—Si—OH* +HCl + C₅H₅N Present Invention: Si—OH* + Si₂Cl₆+ R₃N 3rd ex. embodiment →Si—O—Si(Cl₂)—Si—Cl₃* + HCL + R₃N Si—O—Si(Cl₂)—Si—Cl₃* + R₃N + H₂O →Si—O—Si—O—Si—OH* + HCl + R₃N(Wherein the asterisk* designates the surface species)

Table 2 below is a summary of illustrative combinations of catalyst,first reactant and second reactant corresponding to differentillustrative embodiments of the present invention as describedhereinafter. TABLE 2 2^(nd) Catalyst 1^(st) reactant reactant 1st ex.Ammonia, amine Si₂Cl₆ H₂O, embodiment H₂O_(2,) ozone 2nd ex. Tertiaryaliphatic amine SiCl₄ H₂O, embodiment (R₃N) H₂O_(2,) ozone 3rd ex.Tertiary aliphatic amine Si₂Cl₆ H₂O, embodiment (R₃N) H₂O_(2,) ozone

FIG. 1 is a flow chart that schematically illustrates the several steps,procedures and sequential chemical reactions which apply generically tothe methods of this invention for forming silicon dioxide thin films ona substrate by means of a catalyzed atomic layer deposition (ALD)procedure. The steps illustrated in the flow chart of FIG. 1 arediscussed below.

Step 110

A suitable functionalized substrate is loaded into a reaction chamber.

Step 120

The substrate is preheated until the temperature of the substratereaches a suitable temperature for starting the silicon dioxide ALDprocess, typically about 25°-150° C. The reaction chamber is exhaustedeither at the same time as or immediately following the preheating.Evacuating the chamber might typically take under 60 seconds.

Step 130

A new silicon dioxide layer is formed on the substrate surface by ALD.The cycle is repeated until a desired thickness of a silicon dioxidethin film is grown on the substrate. Step 130 is comprised of substeps132-138, which are discussed individually below.

Steps 132-138

Step 132

A mixture of the first reactant and catalyst is supplied to the reactionchamber. The catalyst acts by lowering reaction activation energy of thefirst reactant on the substrate. As a result, the process temperature islowered to about room temperature or slightly above room temperature.

When the first reactant is supplied, the process temperature in thechamber is typically about 25°-150° C., preferably about 90°-110° C. Theprocess pressure in the chamber is typically about 0.1˜100 torr,preferably about 0.5˜5 torr. An inert gas, for example, argon (Ar), maybe supplied to the chamber along with first reactant and catalyst.

The H of the —OH reaction sites reacts with a halogen atom of the firstreactant in the presence of the first base catalyst to form halogenacid. The halogen acid is neutralized with the first base catalyst, anda salt is produced. At the same time, Si atoms of the first reactantreact with the 0 on a reaction site on the substrate to form achemisorbed layer of the first reactant.

Step 134

By-products of the first reaction process (step 132), for example, salt,unreacted first reactant, etc. are removed.

Step 136

A mixture of the second reactant (which contains O and H) and a secondbase catalyst is now supplied to the chamber causing the chemisorbedlayer of the first reactant to chemically react with the secondreactant.

An example of the second reactant is H₂O, H₂O₂, or ozone. In onepreferred embodiment, the second base catalyst is the same as the firstbase catalyst.

When the second reactant is supplied to the reaction chamber, the rangesof temperature and pressure in the chamber are typically substantiallythe same as the ranges of temperature and pressure used in step 132.

In this step, the O element of the second reactant reacts with Si whichis chemisorbed on the substrate surface. In the presence of the secondbase catalyst, the H element of the second reactant reacts with thehalogen atom, so halogen acid is produced. Salt is then produced byneutralization between such halogen acid and the base catalyst.

Step 138

The by-products of the second reaction process (step 136) are removed.

Step 140

The reaction chamber is exhausted to remove any remaining depositionby-products in the chamber, a step desirably completed in about 90seconds. During step 140, no gas is supplied to the chamber.

Step 150

The substrate with an SiO₂ thin film along its surface is unloaded fromthe chamber.

Step 160

This step involves hardening the newly deposited SiO₂ thin film. Thereare three alternative methods which may be used for hardening thesilicon dioxide layer deposited in accordance with this invention.

-   -   1. Thermal treatment: Annealing the substrate at about 300°        C.-900° C. in the presence of a substantially inert gas (i.e.,        inert relative to the substrate surface), e.g., N₂, O₂, H₂, Ar,        etc.    -   2. Plasma treatment: Annealing the substrate at about 200°        C.-700° C. in the presence of O₂ or H₂.    -   3. O₃ treatment, typically at about 25° C.-700° C.

Any of the three foregoing hardening methods may be used in situ withSiO₂ thin films grown using a catalyzed ALD process in accordance withthis invention. Hardening methods 2 and 3 above have been found to workespecially well.

First Exemplary Embodiment

According to a first exemplary embodiment of the present invention,silicon dioxide thin films are grown on the functionalized surface of asubstrate having hydroxyl groups using Si₂Cl₆ or a comparable compound,e.g., a silicon halide having two or more silicon atoms, as the firstreactant; a compound containing 0 and H elements, e.g., H₂O and/or H₂O₂,as the second reactant; and a base compound, e.g., ammonia or an amine,as the catalyst. For this embodiment of the invention, the firstreactant is a silicon compound having at least two silicon atoms, forexample a silicon-halide compound selected from the group consisting of:Si₂X₆, Si₃X₈, Si₄X₁₀, and Si₃X₆ (Triangle), which has the followingchemical structure:

wherein X is a halogen such as F, Cl, Br, I. In a preferred embodiment,the first reactant is selected from the group consisting of Si₂Cl₆,Si₃Cl₈, Si₄Cl₁₀ and Si₃Cl₆(Triangle). For this embodiment of theinvention, the second reactant is a compound containing oxygen (O) andhydrogen (H) components selected from the group consisting of H₂O; H₂O₂;and ozone.

As schematically illustrated in FIG. 2, by exposing the hydroxyl groupfunctionalized surface of the substrate to a mixture of the firstreactant and the catalyst in a first step, a chemisorbed layer of thefirst reactant is formed along the substrate surface. Unreacted firstreactant and byproducts are then removed from the region of thesubstrate. In the next process step, also illustrated in FIG. 2, thechemisorbed layer of the first reactant is reacted with the secondreactant in the presence of a base compound as the catalyst, which maybe the same catalyst used in reacting the first reactant or a differentbase compound catalyst. Unreacted second reactant and byproducts of thissecond reaction step are removed from the substrate region. The surfaceof the substrate, now containing a new SiO₂ monolayer, is restored tothe hydroxyl group functionalized state ready to begin a new ALD cycle.

Although the foregoing process is generally similar to thecatalyst-assisted ALD technique described in the Klaus '442 patent, theselection of different reactants and catalyst(s) has been found to havedramatic and surprising impacts on the nature and quality of the thinfilm surface layer of the substrate. One important difference is thatwhereas the Klaus '442 patent teaches the use of SiCl₄, a silicon halidehaving only a single silicon atom, the above-described embodiment of thepresent invention utilizes a silicon halide, e.g., Si₂Cl₆, that has atleast two silicon atoms. It has been found in accordance with thisinvention that this difference results in a significant improvement inthe growth rate. In particular, it has been found that a SiCl₄ monolayerhas large spaces between the molecules. In the case of SiCl₄, when a Siatom reacts with the O—H site on the substrate and forms a single bondwith O, SiCl₄ is rotated. Due to the steric hindrance of Cl (which doesnot participate in the reaction), the next O—H site cannot react withanother SiCl₄. By contrast, a Si₂Cl₆ monolayer can react with two Siatoms at the same time and thus speeds up the ALD process. Furthermore,the quality of the resulting silicon dioxide layer is better because themolecular packing along the surface is denser.

FIGS. 3-6, as discussed further below, compare the properties andperformance of SiO₂ monolayers grown on a substrate using thehexachlorodisilicon (HCD) method of this invention with SiO₂ monolayersgrown using the tetrachlorosilicon (TCS) method of Klaus '442.

For example, the graph in FIG. 3 compares the deposition rates of SiO₂monolayers on a substrate utilizing the prior art SiCl₄ approach withthose obtained utilizing the Si₂Cl₆ technique of this invention atvarying process temperatures. FIG. 3 shows that, at every processtemperature, the deposition rate utilizing Si₂Cl₆ (circular points) isapproximately double the deposition rate using SiCl₄ (square points).

FIG. 4 compares the “silicon richness” of a thin film layer grown on asubstrate using the prior art TCS (SiCl₄) approach with that of a thinfilm grown using the HCD (Si₂Cl₆) approach of this invention. UsingAuger electron spectroscopy to measure atomic concentrations of Si and 0on the substrate surface at varying sputter times, FIG. 4 shows that theratio of Si to O using the TCS technique is 1:1.95 while the Si to Oratio using the HCD technique is 1:1.84. In other words, the thin filmSiO₂ layer which is formed using the HCD approach is desirably “richer”in silicon.

FIG. 5A uses XPS data to compare the silicon bonding status of siliconin a SiO₂ monolayer grown using the HCD approach of this invention withthe bonding status of silicon in a monolayer grown using the prior artTCS method. The difference in bonding status seen in the graph of FIG.5A, as well as the difference in silicon “richness” shown by FIG. 4, isbelieved to be explained by the different type of silicon bonds formedwhen the SiO₂ monolayer is grown by the HCD method instead of the TCSmethod. As schematically illustrated in FIG. 5B, the TCS method isbelieved to result in adjacent silicon atoms in a SiO₂ monolayer beingbonded to each other only through an intermediate oxygen atom, whereasthe HCD method of this invention is believed to result in at least somedirect Si—Si bonding in the SiO₂ monolayer.

FIG. 6 compares the wet etch rate of SiO₂ thin films formed using theHCD method of this invention with the wet etch rate for SiO₂ thin filmsformed using the prior art TCS method. (The vertical scale of the bargraph of FIG. 6 has been made discontinuous to accommodate the data.)FIG. 6 shows that the wet etch rate of SiO₂ thin films formed using theHCD method of this invention is about six times better than for SiO₂thin films formed using the TCS method.

Second Exemplary Embodiment

According to a second exemplary embodiment of this present invention,silicon dioxide thin films are grown on a functionalized surface of asubstrate using a silicon halide as the first reactant; a secondreactant containing O and H atoms, e.g., H₂O and/or H₂O₂; and a tertiaryaliphatic amine catalyst. In this embodiment of the invention, byexposing the functionalized surface of the substrate to a mixture of thefirst reactant and the catalyst in a first process step, a chemisorbedlayer of the first reactant is formed along the substrate surface.Unreacted first reactant and byproducts are then removed from the regionof the substrate. In the next process step, the chemisorbed layer of thefirst reactant is reacted with the second reactant in the presence ofthe tertiary aliphatic amine catalyst. Byproducts of this secondreaction step are removed from the substrate region.

In accordance with this invention embodiment, it has been found that theuse of a tertiary aliphatic amine as the reaction catalyst producesnovel and entirely unexpected benefits in terms of process efficiency,the elimination or minimization of unwanted byproducts, and in thepurity and quality of resultant SiO₂ thin films deposited on thesubstrate. More particularly, it has been found that if an amine whichhas even one nitrogen-hydrogen (N—H) bond, for example ammonia (NH₃) ora unitary or binary aliphatic amine (NR, H₂ or NR₂H), is used as thecatalyst, there will be a tendency to form unwanted byproducts havingsilicon-nitrogen (Si—N) bonds, as illustrated in equations (1) and (2)below:SiCl₄+NR₂H→Cl₃Si—NR₂+HClSiCl₄+NH₃→Cl₃Si—NH₄ ⁺Cl⁻(salt)  (2)wherein R is an aliphatic group (C_(x)H_(y)) having between about 1 and5 carbon atoms, and further wherein the aliphatic groups R may be thesame or different.

It has been found, however, that byproducts having Si—N bonds (forexample, as illustrated on the right sides of equations (1) and (2)above) are main causes of particulate formation which leads to surfacelayer impurities and degrades the quality of the deposited SiO₂ thinfilms. By contrast, if a tertiary aliphatic amine catalyst having thegeneral formula NR₃, where R is an aliphatic group (C_(x)H_(y)) havingbetween about 1 and 5 carbon atoms, is used as the reaction catalyst, ithas been found that substantially no particulate byproducts having Si—Nbonds are formed. As a result, much purer SiO₂ thin films having higherquality and superior uniformity are deposited by the methods of thisinvention.

FIG. 7 and Table 3 as discussed below demonstrate the validity and theenormous importance of this finding. FIG. 7 is a result of RGA analysisthat confirms the formation of solid particulate byproducts when an ALDprocess is carried out using an amine catalyst that is not a tertiaryaliphatic amine. FIG. 7 is based on a catalyzed ALD process as taught byKlaus '442 using SiCl₄ as the first reactant with dimethylamine((H₃C)₂NH), an amine with a single N—H bond, as the catalyst. A residualmass spectrum apparatus was connected to the ALD reaction chamber toanalyze byproducts coming from the reaction. The mass spectrum of FIG. 7confirmed the formation of Cl₃Si—N(CH₃)₂ as an unwanted byproduct of thereaction. Such byproduct formation means that some of the Si from theSiCl₄ first reactant is being wasted in forming the byproduct instead ofbeing deposited on the substrate surface as SiO₂.

Further evidence of the advantage of this invention embodiment relativeto the prior art is shown in Table 3 below. TABLE 3 TriethylamineCatalyst Trimethylamine Dimethylamine NH3 Particle Several tens Severalthousands Tens of thousands (size .16 μm) @Tencor

Table 3 compares the number of undesired particles (having a size of atleast 0.16 μm) which were deposited on substrate surfaces of the samearea when catalyzed ALD was carried out using SiCl₄ as a first reactantwith different amines as the catalyst. Table 3 shows that using ammonia(NH₃) as the ALD catalyst, a molecule with three vulnerable N—H bonds,the ALD process resulted in tens of thousands of byproduct particles onthe surface of the SiO₂ thin film. This very high level of particulatecontamination on an SiO₂ thin film adversely affects performance of thesemiconductor device and is completely unacceptable for many of the mostdemanding modern semiconductor applications.

Table 3 also shows that the use of dimethylamine as the ALD catalyst, amolecule with only one vulnerable N—H bond, is effective in somewhatreducing the production of particulate byproduct by about one order ofmagnitude. Even particulate production in the thousands range on an SiO₂thin film, as obtained with dimethylamine catalyst, is still far inexcess of acceptable limits for very high performance semiconductordevices. Table 3 further shows, however, that the use of trimethylamineas the ALD catalyst, thereby eliminating all vulnerable N—H bonds, hasthe dramatic and unexpected result of reducing the production ofparticles of byproduct to only several tens, a three order of magnitudereduction relative to ammonia, and a two order of magnitude reductioneven relative to dimethylamine.

Another advantage of this embodiment of the invention relative to theprior art is that this invention embodiment uses a tertiary aliphaticamine catalyst instead of the pyridine which is the preferred catalystfor example in the Klaus '442 patent. Pyridine is a heterocycliccompound containing a ring of five carbon atoms and one nitrogen atomhaving the formula C₅H₅N. It exists at room temperature as a toxicliquid having a pungent, characteristic odor, which must be carefullyhandled. When used as a catalyst in an ALD process, pyridine must bevaporized to the gaseous state (the boiling point of pyridine is 115.5°C.). Thus, the equipment for treating pyridine is complicated, and apyridine supply line is easily contaminated.

By contrast, a low molecular weight tertiary aliphatic amine, forexample trimethylamine, is a gas at ambient conditions, which makes iteasier to use than a catalyst prone to undergo a phase change at normalreaction conditions. Furthermore, the toxicity of trimethylamine is muchlower than that of pyridine and the boiling point of trimethylamine isonly 3˜4° C.)

Third Exemplary Embodiment

According to a third particularly preferred embodiment of the presentinvention, many if not all of the advantages and benefits of both of theearlier-described embodiments of this invention can be realized. In thisembodiment, silicon dioxide thin films are grown on a functionalizedsurface of a substrate using a silicon compound having at least two ormore silicon atoms, e.g., a silicon halide such as Si₂Cl₆, as the firstreactant; a compound containing O and H atoms, e.g., H₂O and/or H₂O₂, asthe second reactant; and, a tertiary aliphatic amine catalyst.

Thus, in accordance with this invention embodiment, the functionalizedsurface of the substrate is exposed to a mixture of the first reactantand the tertiary aliphatic amine catalyst in a first process step toform a chemisorbed layer of the first reactant along the substratesurface. Unreacted first reactant and any byproducts are then removedfrom the region of the substrate. In the next process step, thechemisorbed layer of the first reactant is reacted with the secondreactant in the presence of the tertiary aliphatic amine catalyst.Byproducts of this second reaction step are removed from the substrateregion.

In still another embodiment of the present invention, it has been foundthat the use of a gas pulsing/purging method for one or more of theseveral process steps 132-138 of FIG. 1 can improve the efficiency ofthe methods of this invention, reduce process contamination, as well asimprove the quality of resulting SiO₂ thin films grown on substrates.FIG. 8 illustrates a gas pulsing method for carrying out steps 132-138of FIG. 1, as described below.

Step 132

A first reactant and a suitable catalyst are flowed into the reactionchamber through separate respective supply lines. At this time, inertgas, for example, argon gas, can be flowed into the chamber through asecond reactant supply line to prevent the contamination from themixture gas of first reactant and a catalyst.

Step 134

Inert gas for purging flows into the chamber through each of the firstreactant supply line, the second reactant supply line, and the catalystsupply line.

Step 136

A second reactant which contains O and H, and a suitable catalyst areflowed into the chamber through separate respective supply lines. Atthis time, inert gas, for example, argon gas, can be flowed into thechamber through the first reactant supply line to purge the firstreactant supply line.

Step 138

Inert gas for purging flows into the chamber through each of the firstreactant supply line, the second reactant supply line, and the catalystsupply line.

Some representative “recipes” or sequences for gas pulsing/pumping orpurging the various feed lines and the reactant chamber in accordancewith steps 132-138 of FIG. 1 over 10 second process time intervals areillustrated in FIGS. 9-12. FIG. 9 illustrates a process purge sequencecomprising the following steps per cycle being conducted at and overselected process time periods using an inert gas to purge and removebyproducts: 0-2 seconds process time—HCD feeding; 2-4 seconds processtime—purging; 4-7.5 seconds process time-H₂O feeding; and 7.5-10seconds—purging. FIG. 10 illustrates a process pumping sequence, whereinthe pumping pressure is lower than the first and second reactant supplypressures, comprising the sequenced steps per cycle of: 0-2 secondsprocess time—HCD feeding; 2-4 seconds process time—pumping; 4-7.5seconds process time—H₂O feeding; and 7.5-10 seconds processtime—pumping. FIG. 11 illustrates a process purge-pumping sequence,wherein pumping is used after purging, comprising the sequences stepsper cycle of: 0-2 seconds process time—HCD feeding; 2-3 seconds processtime—purging; 3-4 seconds process time—pumping; 4-7.5 seconds processtime—H₂O feeding; 7.5-8.5 seconds process time—purging; and 8.5-10seconds process time—pumping. FIG. 12 illustrates a processpumping—purge sequence, wherein purging is used after pumping,comprising the sequenced steps per cycle of: 0-2 seconds processtime—HCD feeding; 2-3 seconds process time—pumping; 3-4 seconds processtime—purging; 4-7.5 seconds process time—pumping; 7.5-8.5 secondsprocess time pumping; and 8.5-10 seconds process time—purging.

In yet another embodiment of the present invention, temperatureconditions for carrying out catalyst-assisted ALD for growing SiO₂ thinfilms on substrates according to this invention are optimized bybalancing two competing process parameters. On the one hand, asillustrated in FIG. 13, the deposition rate for forming SiO₂ thin filmsusing catalyst-assisted ALD and a multiple-silicon atom compound (e.g.,Si₂Cl₆) as the first reactant is inversely proportional to temperature.FIG. 13 shows that, in general, the higher the process temperature, theslower the deposition rate. This appears to be due to desorption rate,and it is a distinctive feature of an ALD process because ALD is asurface reaction. The higher the process temperature, the higher thesurface desorption activation energy of atoms participating in thereaction. As a result, the “staying time” at the surface becomes shorterthan the necessary minimum time for the reaction to take place, inaccordance with the following equation:k _(d) =Ae ^(−E) ^(d) ^(/RT)

-   -   kd: Desorption Rate    -   A: Arrhenius Constant    -   Ed: Desorption Activation Energy        -   R: Gas Constant        -   T: Temperature

The higher the process temperature, the more easily the O—H chain at thesubstrate surface is dehydroxylated. Thus, the number of reaction sitesalong the surface is reduced, and the deposition rate is reduced.

On the other hand, as illustrated in FIG. 14, a SIMS (secondary ion massspectrometer) graph of carbon content over time at three differentprocess temperatures, the carbon content of an ALD-deposited SiO₂ thinfilm also varies according to process temperature. In general, at lowerprocess temperatures, carbon-containing byproducts of the ALD reactionprocesses are not fully removed from the substrate surface duringprocessing and become trapped in the SiO₂ thin films being deposited.The resulting increase in the impurity level of the thin films resultsin a lower quality semiconductor device.

Accordingly, these two process parameters must be balanced against oneanother to optimize the process temperature conditions. Based on theforegoing considerations, it has been determined in accordance with thisembodiment of the invention that the optimum process temperature rangeis about 90°-110° C.

In still another embodiment of the present invention, pressureconditions for carrying out catalyst-assisted ALD for growing SiO₂ thinfilms on substrates according to this invention are optimized bybalancing two competing process parameters. On the one hand, asillustrated in FIG. 15, the deposition rate for forming SiO₂ thin filmsusing catalyst-assisted ALD is directly proportional to processcondition pressure, i.e., the higher the pressure, the thicker the layerof SiO₂ deposited over a given time period/number of ALD cycles.

On the other hand, FIG. 16 illustrates that a non-linear relationshipexists between process pressure and non-uniformity of the SiO₂ thinfilm. Thus, FIG. 16 shows that, up to a point, higher process pressurereduces non-uniformity of the layers deposited; but, beyond that point,higher pressure is correlated with higher non-uniformity.

Accordingly, these process parameters must be balanced against eachother to optimize the process pressure conditions. Based on theforegoing considerations, it has been determined in accordance with thisembodiment of the invention that the optimum process pressure range isabout 500 mmtorr-5 torr.

It will be apparent to those skilled in the art that other changes andmodifications may be made in the above-described improvedcatalyst-assisted ALD formation of SiO₂ thin layers on substratesurfaces for use in high performance semiconductor devices withoutdeparting from the scope of the invention described herein, and it isintended that all matter contained in the above description shall beinterpreted in an illustrative and not a limiting sense.

1-36. (canceled)
 37. A semiconductor device comprising a substratehaving a highly uniform, substantially impurity-free silicon dioxidethin film having enhanced silicon richness along at least a surfacethereof, wherein said silicon dioxide thin film was formed by the stepsof: (a) loading the substrate into a chamber; (b) supplying a firstreactant, a catalyst, and optionally an inert gas to the chamber,wherein said first reactant is a silicon halide compound having at leasttwo silicon atoms and said catalyst is selected from the groupconsisting of ammonia and amine; (c) purging reaction byproducts andunreacted first reactant and catalyst from the chamber; (d) supplying asecond reactant, a catalyst, and optionally an inert gas to the chamber,wherein said second reactant is a compound having 0 components and saidcatalyst is selected from the group consisting of ammonia and amine; (e)purging reaction byproducts and unreacted second reactant and catalystfrom the chamber; and, (f) repeating steps (a)-(e) until the silicondioxide thin film reaches the desired thickness.
 38. A semiconductordevice according to claim 37 wherein the method of forming the silicondioxide thin film further included the step of using a tertiaryaliphatic amine as the catalyst.
 39. A semiconductor device according toclaim 37 wherein the first reactant was Si₂Cl₆.
 40. A method accordingto claim 37 wherein said first reactant is one selected from the groupconsisting of Si₂X₆, Si₃X₈, Si₄X₁₀, and Si₃X₆ (Triangle), wherein X is ahalogen.
 41. A semiconductor device according to claim 37 wherein saidcatalyst is trimethyl amine.
 42. A semiconductor device according toclaim 37 comprising carrying out steps (b) through (e) according to thefollowing sequence: feeding said first reactant and catalyst to saidchamber during a process time period t₁; purging the chamber with aninert gas during a time period t₂ immediately following period t₁;pumping the chamber to at least partially evacuate inert gas and othergaseous materials from the chamber during a time period t₃ immediatelyfollowing period t₂; feeding said second reactant and catalyst to thechamber during a time period t₄ immediately following period t₃; purgingthe chamber with an inert gas during a time period t₅ immediatelyfollowing period t₄; and, pumping the chamber to at least partiallyevacuate inert gas and other gaseous materials from the chamber during atime period t₆ immediately following period t₅.
 43. A semiconductordevice according to claim 37 comprising carrying out steps (b) through(e) according to the following sequence: feeding said first reactant andcatalyst to said chamber during a process time period t₁; pumping thechamber to at least partially evacuate gaseous materials from thechamber during a time period t₂ immediately following period t₁; purgingthe chamber with an inert gas during a time period t₃ immediatelyfollowing period t₂; feeding said second reactant and catalyst to thechamber during a time period t₄ immediately following period t₃; pumpingthe chamber to at least partially evacuate gaseous materials from thechamber during a time period t₅ immediately following period t₄; and,purging the chamber with an inert gas during a time period t₆immediately following period t₅.
 44. A semiconductor device comprisingat least a substrate having a silicon dioxide layer deposited on asurface of said substrate using a catalyst-assisted atomic layerdeposition process comprising the sequential steps of exposing afunctionalized surface of the substrate to a first mixture consistingessentially of first reactant and first catalyst and thereafter exposingthat surface to a second mixture consisting essentially of secondreactant and second catalyst to form a silicon dioxide monolayer on thesubstrate surface, and further comprising one or more of the following:(a) using a first reactant consisting essentially of at least one memberselected from the group consisting of silicon compounds having at leasttwo silicon atoms; (b) using a first catalyst consisting essentially ofat least one member selected from the group consisting of tertiaryaliphatic amine compounds; and, (c) using a first reactant consistingessentially of at least one member selected from the group consisting ofsilicon compounds having at least two silicon atoms in combination withusing a first catalyst consisting essentially of at least one memberselected from the group consisting of tertiary aliphatic aminecompounds.
 45. A semiconductor device according to claim 44 wherein saidfirst reactant used in forming said silicon dioxide layer consistsessentially of a silicon-halide compound.
 46. A semiconductor deviceaccording to claim 44 wherein said first catalyst used in forming saidsilicon dioxide layer consists essentially of a tertiary aliphatic aminecompound having the general formula NR₃, where each R represents thesame or a different aliphatic group having from 1 to 5 carbon atoms. 47.A semiconductor device according to claim 44 wherein said first reactantused in forming said silicon dioxide layer consists essentially ofSi₂Cl₆ and said first catalyst used in forming said silicon dioxidelayer consists essentially of trimethyl amine.
 48. A semiconductordevice formed according to claim 44 wherein the silicon dioxide layerdeposition is carried out at a temperature ranging from about 90°-110°C.
 49. A semiconductor device formed according to claim 44 wherein thesilicon dioxide layer deposition is carried out at a pressure rangingfrom about 500 mmtorr-5 torr.
 50. A semiconductor device formedaccording to claim 44 wherein the silicon dioxide layer depositionfurther includes removing unreacted reactant, catalyst and reactionbyproducts from the region of the substrate surface following eachreaction step.
 51. A semiconductor device formed according to claim 44wherein the silicon dioxide layer deposition further includes: (a) afirst reaction period during which first reactant and catalyst are fedthrough respective first reactant and catalyst feed lines to thesubstrate surface along with inert gas fed through a second reactantfeed line; (b) a first purge period during which the feeds of firstreactant and catalyst are stopped and, instead, inert gas is fed throughthe first and second reactant and catalyst feed lines; (c) a secondreaction period during which second reactant and catalyst are fedthrough their respective feed lines to the substrate surface along withinert gas fed through the first reactant feed line; and, (d) a secondpurge period during which the feeds of second reactant and catalyst arestopped and, instead, inert gas is fed through the first and secondreactant and catalyst feed lines.
 52. A semiconductor device formedaccording to claim 44, further comprising repeating the silicon dioxidelayer deposition multiple times on the same substrate to obtain asilicon dioxide thin film of a desired thickness greater than onemonolayer.
 53. A semiconductor device formed according to claim 44,further comprising hardening the deposited silicon dioxide layer.
 54. Asemiconductor device formed according to claim 53 wherein said hardeningstep is selected from one of the following: (a) a thermal treatmentcomprising annealing the silicon dioxide layer at about 300° C.-900° C.in the presence of an inert gas selected from the group consisting ofN₂, O₂, H₂ and Ar; (b) a plasma treatment comprising annealing thesilicon dioxide layer at about 200° C.-700° C. in the presence of O₂ orH₂; or, (c) an ozone treatment comprising exposing the silicon dioxidelayer to O₃ at a temperature of about 25° C.-700° C.
 55. A substratehaving a silicon dioxide thin film deposited on a surface of saidsubstrate by the steps of: (a) loading the substrate into a chamber; (b)supplying a first reactant, a catalyst, and optionally an inert gas tothe chamber, wherein said first reactant is a silicon-halide compoundhaving at least two silicon atoms and said catalyst is selected from thegroup consisting of ammonia and amine; (c) purging reaction byproductsand unreacted first reactant and catalyst from the chamber; (d)supplying a second reactant, a catalyst, and optionally an inert gas tothe chamber, wherein said second reactant is a compound having Ocomponents and said catalyst is selected from the group consisting ofammonia and amine; (e) purging reaction byproducts and unreacted secondreactant and catalyst from the chamber; and, (f) repeating steps (a)-(e)until the silicon dioxide thin film reaches a desired thickness greaterthan one monolayer.
 56. A substrate formed according to claim 55 whereinsaid first reactant is Si₂Cl₆.